Novel ferrocene derivatives, surfactants containing same and a process for producing organic thin films

ABSTRACT

Ferrocene compounds represented by the formula: ##STR1## wherein A indicates ##STR2## wherein X is --CH 2  --, --O--, ##STR3## G is a hydrogen atom, a methyl group, or an ethyl group, R 4  is a hydrogen atom, a methyl group or an ethyl group, and m is a positive integer satisfying the expression 0≦k+m≦10, Z is --O-- or ##STR4## and R 1  and R 2  are identical or different and each is H, NH 2 , N(CH 3 ) 2 , CH 3 , CH 3  O, OH or a halogen atom, and R 3  is a hydrogen atom or a methyl group, k is a positive integer satisfying the expression 0≦k+m≦10, and n is a real number of 2 to 70, a is an integer of 1 to 4, and b is an integer of 1 to 5. Also provided by the invention are surfactants containing said ferrocene compounds. Further provided is a process which comprises making hydrophobic organic substances soluble in an aqueous medium with the use of a surfactant containing the ferrocene compound described above, and electrolyzing the micelle solution thus obtained to form a thin film of the aforementioned hydrophobic organic substance on the electrode. The ferrocene compounds can be used in various applications including surfactants (micelle forming agents), catalysts, auxiliary fuels, flotating agents, lubricating aides, dispersants, liquid crystals and the like.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to novel ferrocene derivatives,surfactants containing them and a process for producing organic thinfilms, and more particularly to novel ferrocene derivatives having astructure with a main carbon chain bonded to ferrocene skeleton in whichchain an arylene group such as phenylene is contained or a substitutedor unsubstituted phenyl group is bonded as a branch chain; surfactantscontaining the abovedescribed ferrocene derivatives, and capable ofmaking hydrophobic organic substances including phthalocyanine soluble,and a process for producing a thin film of a hydrophobic organicsubstance using these surfactants.

2. Description of the Related Arts

In general, coloring materials such as phthalocyanine or its derivativesare insoluble in water, and although they are soluble in organicsolvents such as dimethylformamide (DMF), tetrahydrofuran (THF) and thelike, their solubility is as small as several milligrams.

Surfactants to dissolve phthalocyanine and the like in water haveheretofore been investigated, but a satisfactory one has not beendeveloped. It is reported that phthalocyanine derivatives substitutedwith a functional group can be dissolved in water to some extent withthe use of sulfone-based surfactants. The solubility therein, however,is not always sufficiently high, and, what is worse, unsubstitutedphthalocyanines are not dissolved at all.

In connection with water-insoluble polymers, surfactants to make themsoluble in water have been investigated similarly to the above, but asatisfactory result has not been obtained.

The present inventors' group have previously developed ferrocenederivatives containing a polyoxyethylene chain as surfactants to makesoluble coloring materials such as phthalocyanine, its derivatives,water-insoluble polymers and the like, and at the same time, they havedeveloped a process for forming an organic thin film by applyingso-called Micellar Disruption Method by use of said ferrocenederivatives (PCT/JP88/00855) published on Mar. 9, 1989 under WO89/01939.

The present inventors have made extensive investigations to develop aprocess for improving the abovementioned surfactants, improving theelectrolytic ability in the Micellar Disruption Method while maintaininga high capability of making hydrophobic organic substances soluble,making the oxidation-reduction reaction of ferrocene derivatives proceedsmoothly, and further improving the productivity of organic thin films.

As the result, it has been found that the object can be attained byferrocene derivatives having a novel structure in which an arylene groupsuch as phenylene group is contained in the substituent of the longchain bonded to the ferrocene skeleton, or a substituted orunsubstituted phenyl group is bonded as branch chain to the long chain.The present invention has been completed based on the findings describedabove.

SUMMARY OF THE INVENTION

An object of the present invention is to provide novel ferrocenederivatives.

Another object of the present invention is to provide surfactants withsuperior properties, containing the abovementioned novel ferrocenederivatives.

A further object of the present invention is to provide a process forefficiently producing a hydrophobic organic thin film.

The present invention provides novel ferrocene derivatives representedby the general formula: ##STR5## wherein A indicates ##STR6## wherein Xis --CH₂ --, --O--, ##STR7## G is a hydrogen atom, a methyl group, or anethyl group, R⁴ is a hydrogen atom, a methyl group, or an ethyl group,and m is a positive integer satisfying the expression (1) describedbelow, Z is --O-- or ##STR8## R¹ and R² are each H, NH₂, N(CH₃)₂, CH₃,CH₃ O, OH or a halogen atom, and R³ is a hydrogen atom or a methylgroup, k is a positive integer satisfying the expression:

    0≦k+m≦10                                     (1),

and n is a real number of 2 to 70, a is an integer of 1 to 4, and b isan integer of 1 to 5.

The novel ferrocene derivatives represented by the above general formula(α) are divided into two kinds represented by the following formulae (I)and (II).

That is, novel ferrocene derivatives represented by the general formula(I): ##STR9## wherein each symbol is as defined above, however, k is apositive integer satisfying 0≦k≦10 (when m=0 in the beforementionedexpression)

or

novel ferrocene derivatives represented by the general formula (II):##STR10## wherein each symbol is defined as above.

Moreover, the present invention provides surfactants containing thenovel ferrocene derivatives represented by the general formula (α).Furthermore, the present invention provides a process for solubilizinghydrophobic organic substances, which comprises making hydrophobicorganic substances soluble with the use of a surfactant containing theabovementioned novel ferrocene derivatives in an aqueous medium, and aprocess for producing an organic thin film, which compriseselectrolyzing the micelle solution resulting from the said solubilizingprocess, to form a thin film of the above hydrophobic organic substanceon an electrode.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 shows a ¹ H-NMR spectrum of the ferrocene derivative obtained inExample 1, and FIG. 2 and FIG. 3 show a ¹ H-NMR spectrum of theferrocene derivative obtained in Example 2 and Example 3, respectively.

FIG. 4 shows a visible absorption spectrum of the supernatant obtainedand a visible absorption spectrum of the thin film formed on ITO inExample 4. FIGS. 5 and 6 show visible absorption spectrums of thesupernatant and of the thin film formed on ITO in Examples 5 and 6,respectively.

FIGS. 7 to 9 show a ¹ H-NMR spectrum of the ferrocene derivativeobtained in Examples 7, 8 and 9, respectively.

FIG. 10 shows a ¹ H-NMR of the ferrocene derivative obtained in Example13, and FIG. 11 shows a ¹ H-NMR of the ferrocene derivative obtained inExample 15.

DESCRIPTION OF PREFERRED EMBODIMENTS

The ferrocene derivatives of the present invention are represented bythe general formula (α), more specifically by the general formula (I) or(II).

First, in the ferrocene derivatives represented by the general formula(I), each symbol in the general formula (I) is as mentioned above. Amongthem, R¹ and R² are independently a hydrogen atom (H), a methyl group(CH₃), a methoxy group (OCH₃), an amino group (NH₂), a dimethylaminogroup (N(CH₃)₂), a hydroxy group (OH) or a halogen atom (chlorine,bromine, fluorine, etc.), R¹ and R² may be identical or different, andin case where a plural number of R¹ and R² are present at a 5-memberedring of ferrocene, the plural R¹ and R² may be identical or differentfrom each other. The symbol n indicates a recurring number of anoxyethylene group or 1-methyloxyethylene group such as an integer of 2.0to 70.0 but also a real number including these, and indicates an averagevalue of recurring numbers of the oxyethylene group or1-methyloxyethylene group.

The novel ferrocene derivatives represented by the above general formula(I) can be produced by various methods. Specifically, these methods canbe broadly divided into the following three. These processes forproduction are shown by the reaction formulae as follows.

Method 1 ##STR11## X¹ is a halogen atom, and R is a methyl group or anethyl group. ##STR12##

In the reactions up to here, Step (i) is preferably carried out in thetemperature range of 0° C. to the reflux temperature in the presence ofLewis acids such as AlCl₃, SbCl₅, FeCl₃, FeCl₂ and SnCl₄, with the useof the solvents such as methylene chloride, carbon disulfide, carbontetrachloride, and ethylenedichloride. In Step (ii), the reaction ispreferred to proceed at room temperature to reflux temperature in thepresence of AlCl₃, NaBH₄ or the like, using the solvents such astetrahydrofuran (THF) and dioxane.

Next, the compound represented by the general formula (I - II) thusobtained is reacted with a compound: ##STR13## X² is ##STR14## or ahalogen such as Br Herein when X² is ##STR15## the following reactionsproceed. ##STR16##

As the result of this reaction, the desired product (I - 1) is obtained.In Step (iii), solvents such as diethylether, THF and dioxane arepreferably used, with the use of bases such as triethylamine, pyridine,lutidine and collidine. In Step (iv), it is preferred that dehydrationor trans-esterification proceeds while heating by use of potassiumt-butoxide, potassium cyanide or sulfuric acid as a catalyst, andfurther, it is effective to use molecular sieves in order to removealcohol and other byproducts resulting in the system.

When X² in the general formula (I - III) is Br, the following reactionsproceed. ##STR17##

As the result of the above reaction, the desired product (I - 2) isobtained. Therein, in Step (v), it is preferable to use alkali metals(Na, K), bases such as triethylamine, pyridine, lutidine and collidine,and to employ CuI or CuBr as the catalyst.

Method 2 ##STR18##

In the reaction up to here, Step (i) is as mentioned before, and in Step(vi), it is preferred to use alkalis such as KOH and NaOH, and to usesolvents such as methanol and ethanol. In Step (vii), further, it ispreferred to use common catalysts for a Clemmensen reduction, and to usemethanol, ethanol, toluene or acetic acid as the solvents.

The compound of the general formula (I - VI) thus obtained is furthersubjected to the following reaction. ##STR19## (D is a halogen atomincluding Br, or CO₂ Q (Q is a hydrogen atom, a methyl group or an ethylgroup) ##STR20##

In Step (viii), preferred solvents are methylene chloride, ethylenedichloride or the like, and a preferred example of the condensing agentis 1,3-dicyclohexylcarbodiimide.

Subsequently, the compound represented by the general formula (I - VII)is reacted with a compound: ##STR21##

In the general formula (I - VII), when D is a halogen atom includingbromine, as the result of a reaction with the use of alkali metals (Na,K) as well as the bases such as triethylamine, pyridine, lutidine andcollidine, and using CuI, CuBr or the like as the catalyst, a compound:##STR22## is obtained.

In the general formula (I - VII), in the case where D is CO₂ Q, whendehydration or trans-esterification is effected using potassiumt-butoxide, potassium cyanate or sulfuric acid as the catalyst, and,further, molecular sieves and the like to remove alcohol and otherbyproducts resulting from the reaction system, then a compound:##STR23## is obtained.

Method 3 ##STR24##

In the above reactions, all of Steps (i), (vi) and (vii) are asmentioned before. Further, by way of the reaction: ##STR25## the desiredcompound represented by the general formula (I - 5) is obtained. In Step(ix), dehydration condensation or trans-esterification proceeds.

Method 4 ##STR26##

In the reactions up to here, Step (i) is as mentioned before, butfurther solvents such as benzene halide (or its derivatives) andnitrobenzene which are reaction materials can be used also. Step (vii)is as mentioned above, but also dimethoxyethane can be used as thesolvent. In Step (x), it is preferred to use SOCl₂, PCl₃ or (COCl)₂ as acatalyst, and to reflux at room temperature to 100° C. for about 30minutes to 6 hours, without a solvent or in a solvent such as benzene ordimethyl formamide (DMF).

Subsequently, the compound represented by the general formula (I - IX)is reacted with a compound of the formula: ##STR27## in the sameconditions as in Step (i) described above, to obtain a compoundrepresented by the formula: ##STR28## Further, a Clemmensen reduction iseffected in the same manner as in Step (vii) mentioned before, toproduce a compound of the formula: ##STR29## which is reacted with acompound: ##STR30## with the use of alkali metals (Na, K) and bases suchas triethylamine, pyridine, lutidine and collidine, and at the same timeusing CuI or CuBr as a catalyst, to obtain the desired compoundrepresented by the formula: ##STR31##

Method 5

With the compound represented by the general formula (I - X), CuCN orNaCN is reacted in the solvents such as DMF, N,N-dimethylformamide andhexamethylphosphoric triamide (HMPA), to obtain a compound of theformula: ##STR32## Therein, above reaction proceeds also withoutsolvents, and use of a catalyst including ferric chloride is alsoeffective. As the reaction, it is sufficient to reflux at thetemperature of 100° to 300° C. for a reaction period of about 3 to 20hours.

Subsequently, the compound of the general formula (I - XI) is reactedwith caustic alkali (KOH, NaOH, Ba(OH)₂) or concentrated hydrochloricacid for 1 to 20 hours in the reflux conditions of room temperature to200° C., in the mixed solvent of water and ethanol, the mixed solvent ofwater and ethylene glycol, or the mixed solvent of water and diethyleneglycol, to obtain a compound of the formula: ##STR33## After that, theabove compound is reacted with a compound represented by the formula:##STR34## in the presence of a catalyst such as sulfuric acid andp-toluene sulfonic acid, to obtain the desired compound: ##STR35##

Method 6 ##STR36##

Therein, Step (xi) is almost the same as beforementioned Step (i). Step(xii) is identical to the reaction of the Clemmensen reduction in Method4 described before. In Step (xiii), the reaction is carried out at 50°to 100° C. for 1 to 30 hours, using a phase-transfer catalyst such as C₄H₉ N⁺ BF₄ ⁻ or C₆ H₅ CH₂ N⁺ (C₂ H₅)₃ Cl⁻, with sodium azide in aqueoussolution. In Step (xiv), hydrogenation is preferably effected in therange of 0° C. to the reflux temperature with the use of a solvent suchas diethylether, THF and dioxane, in the presence of LiAlH₄.

The compound represented by the general formula (I - XII) thus obtainedis further subjected to the following reactions. ##STR37##

Herein, the reaction in Step (xv) is carried out in an aprotic solventsuch as toluene, ether and methylene chloride, in the presence of atertiary amine catalyst such as triethylamine and pyridine or without acatalyst, at a temperature of -15 to 50° C. for 30 minutes to 8 hours.Step (xvi) is a hydrolysis, which is a reaction at room temperature to100° C. for 30 minutes to 5 hours, in the presence of caustic alkali(KOH, NaOH, LiOH, etc.) in ethanol, methanol or water as a solvent. Step(xvii) is a reaction at 50° to 200° C. for 3 to 30 hours in the presenceof a catalyst such as sulfuric acid and p-toluenesulfonic acid.

According to those methods as above, the novel ferrocene derivativesrepresented by the general formula (I) (including the general formulae(I - I) to (I - 8)) can be obtained.

Next, the novel ferrocene derivatives represented by the beforementionedgeneral formula (II) will be explained. Each symbol in the generalformula (II) is as defined before.

R⁴ indicates a hydrogen atom, a methyl group (CH₃), or an ethyl group(CH₂ CH₃). The position of substitution may be any of o-, m- orp-position. Z is an oxygen atom (--O--) or an oxycarbonyl group##STR38## R³ is a hydrogen atom or a methyl group (CH₃) as mentionedbefore.

Accordingly, the general formula: ##STR39## represents: ##STR40##

In the length of the main carbon chain having a substituted orunsubstituted phenyl group, bonded to a 5-membered ring of the ferroceneskeleton, that is: ##STR41## k and m are each a positive integersatisfying 0≦k+m≦10. k is preferably 1 to 5, and m is preferably 1 to 5.Ferrocene derivatives in which k+m is in excess of 10 become poor inelectrolytic property.

In the compound of the present invention, the above described maincarbon chain is bonded with: ##STR42## as a branched chain.

Such novel ferrocene derivative represented by the general formula (II)can be produced b y various methods. Specifically, when Z is anoxycarbonyl group ##STR43## a substituted or unsubstituted ferrocenerepresented by the general formula: (wherein R¹, R², a and b are asdefined above) is reacted in solvents such as methyl chloride, carbondisulfide, carbon tetrachloride and nitrobenzene, with a dicarboxylicacid anhydricde having a substituted or unsubstituted phenyl group,represented by the general formula: ##STR44## (wherein R⁴, k and m areas defined above) in the presence of a Friedel-Crafts catalyst (forexample, AlCl₃, FeCl₂, FeCl₃, SbCl₅ and SnCl₄), at -20° C. to the refluxtemperature, to obtain a compound represented by the general formula:##STR45## wherein R¹, R², R⁴, a, b, k and m are as defined above). Thenthe compound represented by the above general formula (II - IV) issubjected to a Clemmensen reduction at 20° to 120° C., in the solventssuch as alcohol (methanol or ethanol), dimethyl ether, toluene, andacetic acid, using zinc or zinc amalgam and concentrated hydrochloricacid as the reductant, to obtain a compound represented by the generalformula: ##STR46## R¹, R², R⁴, a, b, k and m are as defined above).

After that, the compound of (II - V) is subjected todehydration-condensation with a polyethylene glycol compound representby: ##STR47## (n and R³ are as defined above), that is HO(CH₂ CHO)_(n) Hor ##STR48## in the catalyst such as p-toluene sulfonic acid andsulfuric acid, to produce the desired novel ferrocene derivativesrepresented by the general formula: ##STR49## (wherein R¹, R², R³, R⁴,a, b, k, m and n are as defined above).

For example, in the case where Z is an oxygen atom (--O--), the compoundrepresented by the general formula (II - II) is reacted with a compoundrepresented by the general formula; ##STR50## (wherein R⁴, k and m areas defined above) in the same conditions as in the beforedescribedreaction of the compounds represented by the general formulae (II - II)and (II - III) to obtain the compound represented by the generalformula: ##STR51## (wherein R¹, R², R⁴ a, b, k, and m are as definedabove).

subsequently, the compound represented by the general formula (II - IV')is esterificated with methyl alcohol or ethyl alcohol by refluxing for 3to 10 hours in the catalysts such as p-toluene sulfonic acid or sulfuricacid, to obtain a compound represented by the general formula (II - VI):##STR52## (wherein R¹, R², R⁴, a, b, k and m are as defined above, andR⁶ indicates a methyl group or an ethyl group).

Further, the compound having the general formula (II - VI) is refluxedfor 0.5 to 10 hours in an aprotic polar solvent such as tetrahydrofuran,1,4-dioxane, diethylether, and dimethylether, in the presence ofreductants such as sodium borohydride (NaBH₄) or lithium aluminumhydride (LiAlH₄), to obtain the compound represented by the generalformula: ##STR53## (wherein R¹, R², R⁴, a, b, k and m are definedabove).

Subsequently, the compound represented by the general formula (II - VII)is halogenated with carbon tetrachloride or carbon tetrabromide byrefluxing for 0.5 to 6 hours in a chloroform solvent, in the presence oftriphenylphosphine, to obtain a compound represented by the generalformula: ##STR54## (wherein R¹, R², R⁴, a, b, k and m are as definedabove, and Y indicates chlorine or bromine). In that reaction, in thecase where carbon tetrachloride is used as a reaction material, saidcarbon tetrachloride can be used as a solvent.

The compound of the general formula (II - VIII) obtained through theabovementioned reaction is reacted with the polyethylene glycol compoundrepresented by the formula: ##STR55## (n and R³ are as defined above.),at 50° to 200° C. for 3 to 30 hours in the presence of alkali metalssuch as sodium, lithium and potassium, to obtain the novel ferrocenederivatives represented by the general formula: ##STR56## (wherein R¹,R², R³, R⁴, a, b, k, m and n are as defined above).

The novel ferrocene derivatives of the present invention obtained by theabovedescribed processes are useful as surfactants, and can be usedparticularly as surfactants for making hydrophobic organic substancessoluble into aqueous media (micelle forming agents). When used asmicelle forming agents, the ferrocene derivatives of the presentinvention can be used singly or in a mixture of several ferrocenederivatives.

The surfactant of the present invention contains, as main components,the ferrocene derivatives represented by the above general formula (α),among them, the general formulae (I), (II) (including the abovementionedgeneral formulae (I - I) to (I - 8), (II'), (II")), and variousadditives can be added thereto appropriately, if necessary.

The surfactant of the present invention is capable of making varioushydrophobic organic substances soluble into aqueous media. There arevarious hydrophobic organic substances. Specific examples are, as wellas coloring materials for optical memory and organic coloring materialssuch as phthalocyanine, metal complexes thereof, and derivativesthereof, naphthalocyanine, metal complexes thereof and derivativesthereof, porphyrin and its metal complexes, and derivatives thereof;electrochromic materials such as 1,1- diheptyl-4,4'-bipyridiniumdibromide, 1,1'-didodecyl-4,4'- bipyridinium dibromide and the like;light sensitive materials (photochromic materials) and light sensormaterials such as6-nitro-1,3,3-trimethylspiro-(2'H-1'-benzopyran-2,2'-indoline) (commonlycalled spiropyran) and the like; liquid crystal display coloringmaterials such as p-azoxyanisole and the like. Further examples are thehydrophobic compounds among the coloring materials each for electronics,recording, light sensitive chromism, photos, energy use, biomedicals,and coloring materials for food and cosmetics, dyes, coloring mattersfor specific coloring which are listed in "Color Cyclopedia", CMC Co.,Ltd., pp 542-717, Mar. 28, 1988. Moreover, other examples areelectrically conductive organic materials and gas sensor materials suchas the 1:1 complex of 7,7,8,8-tetracyanoquinonedimethane (TCNQ) andtetrathiafulvalene (TTF), light curing paints such as pentaerythritoldiacrylate and the like, insulating materials such as stearic acid andthe like, diazo-type light-sensitive materials and paints such as1-phenylazo-2-naphthol and the like. Still further examples arewater-insoluble polymers, for examples, general purpose polymers such aspolycarbonate, polystyrene, polyethylene, polypropylene, polyamide,polypheylene sulfide (PPS), polypheylene oxide (PPO), polyacrylonitrile(PAN) and the like, polypheylene, polypyrrole, polyaniline,polythiophene, acetyl cellulose, polyvinyl acetate, polyvinyl butyral,and various polymers (polyvinyl pyridine and the like) and copolymers (acopolymer of methyl methacrylate and methacrylic acid).

In the case where the ferrocene derivatives of the present invention areused as surfactants, there are various embodiments. Particularly in theproduction of the organic thin film of the present invention, they areeffectively used as micelle forming agents. In the process of thepresent invention, a surfactant (micelle forming agent, concentrationnot lower than the limit micelle concentration) comprising a ferrocenederivative represented by the general formula (α), particularly (I) or(II), a supporting salt, and a hydrophobic organic substance are placedin aqueous media and thoroughly dispersed by the use of supersonicwaves, a homogenizer, or a stirrer, for example, to form a micelle. Thisdispersion is conducted usually for 1 hour to 10 days. Thereafter, ifnecessary, an excessive hydrophobic organic substance is removed, andthe micelle solution thus obtained is subjected to electrolytictreatment using the undermentioned electrode while allowing it to standor stirring it somewhat. During the electrolytic treatment, ahydrophobic organic substance may be supplementally added to the micellesolution, or there may be provided a recycle circuit in which themicelle solution in the vicinity of the anode is withdrawn from thesystem, a hydrophobic organic substance is added to the withdrawnmicelle solution and thoroughly stirred, and then the resulting solutionis returned to the vicinity of the cathode. Electrolytic conditions aredetermined appropriately depending on various circumstances. Usually,the liquid temperature is 0° to 70° C. and preferably 20° to 30° C., thevoltage is 0.03 to 100 V and preferably 0.15 to 0.7 V, and the currentdensity is not more than 10 mA/cm², preferably 50 to 300 μA/cm².

On performing this electrolytic treatment, the oxidation-reductionreaction of the ferrocene derivatives proceeds. In connection with thebehavior of the Fe ion in the ferrocene derivative, Fe²⁺ is convertedinto Fe³⁺ on the anode, leading to the breakdown of the micelle, andparticles (about 600 to 900 Å) of a hydrophobic organic substance aredeposited on the anode. On the other hand, Fe³⁺ oxided on the anode isreduced to Fe²⁺ on the cathode, recovering the original micelle and,therefore, a film forming operation can be carried out repeatedly usingthe same solution.

Since the novel ferrocene derivatives used in the process of the presentinvention contain arylene groups such as phenylene group in the maincarbon chain, or possess a substituted or unsubstituted phenyl groupbonded to the main carbon chain as the branch chain, they have a highability to make hydrophobic substances soluble, and the beforementionedoxidation-reduction reaction proceeds very efficiently in the saidferrocene derivatives, and accordingly, a thin film can be formed in ashort time.

Electrolytic treatment as described above forms a thin film composed ofabout 600 to 900 Å particles of the desired hydrophobic organicsubstance on the anode.

The supporting salt (supporting electrolyte) to be used in the processof the present invention is added, if necessary, in order to control theelectrical conductance of the aqueous medium. The amount of thesupporting salt added is usually about 0 to 300 times, preferably about10 to 200 times that of the above surfactant (micelle forming agent).Said supporting salt is not always necessary for electrolysis. When thesupporting salt is not used, a film of high purity, containing nosupporting salt can be obtained. In case a supporting salt is used, thetype of the supporting salt is not critical as long as it is capable ofcontrolling the electric conductance of the aqueous medium withoutinhibiting the formation of the micelle and the deposition of the abovehydrophobic organic substance.

More specifically, sulfuric acid salts (salts of lithium, potassium,sodium, ribidium or aluminum) and acetic acid salts (salts of lithium,potassium, sodium, ribidium, beryllium, magnesium, calcium, strontium,barium or aluminum), halides, (salts of lithium, potassium, sodium,rubidium, calcium, magnesium, or aluminum), and water-soluble oxidesalts (salts of lithium, potassium, sodium, rubidium, calcium, magnesiumor aluminum), which are generally widely used as supporting salts, aresuitable.

The electrode to be used in the process of the present invention issufficient to be a metal more noble than the oxidation potential(against +0.15 V saturated calomel electrode) of ferrocene, or anelectrically conductive substance. Specific examples are ITO (mixedoxide of indium oxide and tin oxide), platinum, gold, silver, glassycarbon, electrically conductive metal oxides, electrically conductiveorganic polymers and the like.

The ferrocene derivatives of the present invention are novel compoundsand can be used in various fields, for example, as surfactants (micelleforming agent), catalysts, auxiliary fuels, flotation agents,lubricating aids, dispersants, liquid crystals and the like. The novelferrocene derivatives, when used as surfactants (micelle formingagents), form micelles in an aqueous solution system and, therefore, canmake soluble various hydrophobic organic substances such as coloringmaterials including phthalocyanine, having a wide variety ofapplications and water-insoluble polymers.

According to the process of the present invention, in which ferrocenederivatives are added as surfactants (micelle forming agents) and thegathering or scattering of micelles by aqueous solution electrolysis areutilized, an organic thin film extremely small in thickness can beformed. In this process, the film is formed in a very high productivitysince the oxidation-reduction efficiency of the said surfactant isexcellent.

The organic thin film formed according to the process of the presentinvention can be effectively utilized in various fields includingphotoconductor materials, light-sensitive materials and solar batteries.

The present invention will be explained in more detail by referring toExamples and Comparative Examples.

PREPARATION EXAMPLE 1

(1) An acid chloride prepared by reacting 25.0 g of glutaric monomethylester and 50.0 ml of thionyl chloride was reacted with 34.0 g ofaluminum chloride and 31.8 g of ferrocene at 50° C. for 3 hours in amethylene chloride solvent.

After completion of the reaction, the reaction mixture was treated withwater, extracted with ethyl acetate, and then purified with a silcia gelcolumn chromatogrtaphy to obtain 38.8 g of methyl-4-ferrocenoyl butyraterepresented by the following formula: ##STR57## (2) An amount of 38.8 gof methyl-4-ferrocenoyl butyrate prepared in (1) above, 54.7 g ofaluminum chloride and 25.9 g of sodium borohydride were heat-refluxedfor 2 hours in a tetrahydrofuran solvent.

After completion of the reaction, the reaction mixture was treated withdilute hydrochloric acid, extracted with ethyl acetate and purified witha silica gel column chromatography to obtain 22.0 g of 5-ferrocenylamylalcohol represented by the following formula: ##STR58## (3) An amount of2.7 g of 5-ferrocenylamyl alcohol obtained in (2) above, 1.9 g ofterephthaloyl monomethoxy monochloride and 1.4 ml of triethylamine werestirred in ether at room temperature for 2 hours, to obtain 3.2 g ofp-(5-ferrocenylamyloxycarbonyl)-benzoic acid methyl ester represented bythe formula: ##STR59##

EXAMPLE 1

An amount of 2.7 g of p-(5-ferrocenylamyloxycarbonyl)benzoic acid methylester prepared in Preparation Example 1 was reacted with 30.0 g ofpolyethylene glycol (average molecular weight: 600), 5 g of molecularsieves 5A and 0.01 g of potassium tert-butoxide, at 80° C. for 5 hours.

After completion of the reaction, the reaction mixture was treated withwater, and extracted with n-butanol saturated with water. Subsequentlythe extract was concentrated, and subjected to a silica gel columnchromatography by the use of a mixed solvent of ethyl acetate andmethanol (ethyl acetate : methanol=3:1), to obtain 2.83 g of the desiredproduct in a yield of 45%.

The elemental analytical values of the product were: carbon, 58.9%;hydrogen, 7.3%; nitrogen, 0.0%. The results of measurement of protonnuclear magnetic resonance (¹ H-NMR) spectrum are as shown in FIG. 1.

From the above results, it can be seen that the above resulting compoundwas a ferrocene derivative having the following structure: ##STR60##

PREPARATION EXAMPLE 2

(1) In the presence of 11.2 g of anhydrous aluminum chloride, 14.1 g offerrocene and 15.0 g of terephthaloyl monomethoxy monochloride werereacted at room temperature for 2 hours in a methylene chloride solvent.

After completion of the reaction, the reaction mixture was treated withdilute hydrochloric acid and then purified with a silica gel columnchromatography to obtain 12.6 g of methyl-p-ferrocenoyl benzoaterepresented by the formula: ##STR61## (2), An amount of 6.3 g ofmethyl-p-ferrocenoyl benzoate prepared in (1) above and 1.8 g ofpotassium hydroxide were refluxed for 2 hours in an ethanol solvent andthen subjected to acid treatment to obtain 6.0 g of p-ferrocenoylbenzoic acid represented by the formula: ##STR62## (3) In the presenceof zinc amalgam prepared from 6.5 g of zinc and 2.7 g of mercuricchloride, 6.0 g of p-ferrocenoyl benzoic acid prepared in (2) above wasreacted at 80° C. for 3 hours in a mixed solvent of concentratedhydrochloric acid and ethanol.

After completion of the reaction, the reaction mixture was extractedwith ethyl acetate and purified with a silica gel column chromatographyto obtain 3.0 g of p-ferrocenylmethyl benzoic acid ethyl esterrepresented by the formula: ##STR63##

EXAMPLE 2

An amount of 1.0 g of p-ferrocenylmethyl benzoic acid ethyl esterprepared in Preparation Example 2 and 29.0 g of polyethylene glycol(average molecular weight : 1000) were reacted with 0.2 ml ofconcentrated sulfuric acid, at 110° C. for 10 hours.

After completion of the reaction, the reaction mixture was washed withwater, extracted with n-butanol saturated with water, and theconcentrated extract was purified with a silica gel columnchromatography using a mixed solvent of ethyl acetate and methanol(ethyl acetate : methanol=3:1), to obtain 1.3 g of the desired substancein a yield of 30.2%.

The elemental analytical values were: carbon, 58.2%; hydrogen, 8.3%;nitrogen, 0.00%. The results of measurement of proton nuclear magneticresonance spectrum were as shown in FIG. 2.

These results show that the product was a ferrocene derivative havingthe following structure: ##STR64##

PREPARATION EXAMPLE 3 (1) An amount of 25.8 g of methyl-4-ferrocenoylbutyrate prepared according to the method of Preparation Example 1 (1)was reacted in ethanol with 11.5 g of potassium hydroxide, to obtain24.0 g of 4-ferrocenoyl butyric acid represented by the followingformula: ##STR65## (2) In the presence of zinc amalgam prepared from52.3 g of zinc and 21.7 g of mercuric chloride, 24.0 g of 4-ferrocenoylbutyric acid prepared in (1) above was reacted at 80° C. for 3 hours ina mixed solvent of concentrated hydrochloric acid and ethanol.

After completion of the reaction, the reaction mixture was extractedwith ethyl acetate and purified with a silica gel column chromatographyto obtain 16.0 g of 5-ferrocenoyl valeric acid represented by theformula: ##STR66## (3) To 16.0 g of 5-ferrocenoyl valeric acid preparedin (1) above, 12.0 g of 1,3-dicyclohexylcarbodiimide was added in adichloroethane solvent. Further, 7.7 g of p-aminobenzoic acid was addedto the resulting mixture, and reacted while heating from 0° C. to thereflux temperature.

After completion of the reaction, the reaction mixture was extractedwith ethyl acetate and purified with a silica gel column chromatography,to obtain 10.9 g of N-(p- carboxyphenyl)-5-ferrocenyl valeric acid amiderepresented by the formula: ##STR67##

EXAMPLE 3

The procedure of Example 2 was repeated except that 10.9 g ofN-(p-carboxyphenyl)-5-ferrocenyl valeric acid amide prepared inPreparation Example 3, 134.0 g of polyethylene glycol (average molecularweight : 600) and 2.0 ml of concentrated sulfuric acid were used.

The amount of the resulting compound was 8.7 g, and the yield was 32%.Elemental analytical values of that substance were: carbon, 54.0%;hydrogen, 7.4%; nitrogen, 0.01%, and the results of measurement ofproton nuclear magnetic resonance spectrum was as shown in FIG. 3.

These results show that the purified product was a ferrocene derivativehaving the following structure: ##STR68##

EXAMPLE 4

Into 100 cc of water, the ferrocene derivative obtained in Example 1 asa surfactant (micelle forming agent) was added to make 2 mM solution.Then 0.1 g of phthalocyanine was added to 20 cc of said solution anddispersed by stirring with supersonic waves for 10 minutes, to form amicelle. Further, after the mixture was stirred for two days and nightsby a stirrer, the resulting micelle solution (dispersed solution) wassubjected to centrifugal separation at 2,000 rpm for 30 minutes.

A visible-absorption spectrum of the supernatant is shown in FIG. 4(Mark A). This confirmed that phthalocyanine was soluble (dispersed) inthe micelle solution. The solubility of phthalocyanine was 9.8 mM/2 mMmicelle forming agent solution.

Into the above solution, lithium bromide as a supporting salt was addedso that the concentration may be 0.1 M, and stirred for 10 minutes bythe use of a stirrer.

With the use of this micelle solution as an electrolyte, ITO transparentglass electrode as the anode, platinum as the cathode and a saturatedcalomel electrode as a reference electrode, constant electric potentialelectrolysis was carried out at 25° C. at the applied voltage of 0.5 Vand an electric current density of 12 μA/cm² for 30 minutes. The amountof electricity passed in that period was 0.02 coulomb (C).

As the result, a thin film of phthalocyanine was formed on the ITOtransparent glass electrode. A visible absorption spectrum ofphthalocyanine on the ITO transparent glass electrode is shown in FIG. 4(Mark B). Since FIG. 4 (Mark A) agreed with FIG. 4 (Mark B), it wasconfirmed that the thin film on the ITO transparent glass electrode wasphthalocyanine. An ultraviolet (UV) absorption spectrum showed that thethickness of the thin film was 1.1 μm.

Further, as the result of cyclic voltammetry, the oxidation-reductionpotential was 0.213 V, and the difference between the peak potentials ofoxidation and reduction was 95 mV, which shows that the efficiency ofoxidation-reduction was improved compared with that in ComparativeExample 1 to be mentioned later.

EXAMPLE 5

The ferrocene derivative obtained in Example 2 as a surfactant (micelleforming agent) was added into 100 cc of water to make 2 mM solution.Then 0.1 g of phthalocyanine was added to 20 cc of said solution, anddispersed by stirring for 10 minutes with supersonic waves to make amicelle. The mixture was further stirred for two days and nights with astirrer, and then the micelle solution (dispersed solution) thusobtained was subjected to centrifugal separation at 2,000 rpm for 30minutes.

A visible absorption spectrum of the supernatant obtained is shown inFIG. 5 (Mark A). This confirmed that phthalocyanine was soluble(dispersed) in the micelle solution. The solubility of phthalocyaninewas 7.2 mM/2 mM micelle forming agent solution.

Into this solution, lithium bromide as a supporting salt was added sothat the concentration would be 0.1 M, and stirred for 10 minutes with astirrer.

With the use of said solution as an electrolyte, an ITO transparentglass electrode as an anode, platinum as a cathode and a saturatedcalomel electrode as a reference electrode, constant electric potentialelectrolysis was carried out at 25° C. at the applied voltage of 0.5 Vand an electric current density of 15 μA/cm² for 30 minutes. The amountof electricity passed in that period was 0.03 C.

As the result, a thin film of phthalocyanine was formed on the ITOtransparent glass electrode. A visible absorption spectrum ofphthalocyanine on the ITO transparent glass electrode is shown in FIG. 5(Mark B). Since FIG. 5 (Mark A) agreed with FIG. 5 (Mark B), it wasconfirmed that the thin film on the ITO transparent glass electrode wasphthalocyanine. A UV absorption spectrum showed that the thickness ofthe thin film was 0.7 μm.

Further, as the result of cyclic voltammetry, the oxidation-reductionpotential was 0.205 V, and the difference between the peak potentials ofoxidation and reduction was 85 mV, which shows that the efficiency ofoxidation-reduction was improved compared with that in ComparativeExample 1 to be mentioned later.

EXAMPLE 6

The ferrocene derivative obtained in Example 3 as a surfactant (micelleforming agent) was added into 100 cc of water to make 2 mM solution.Then 0.1 g of phthalocyanine was added to 20 cc of said solution anddispersed by stirring for 10 minutes with supersonic waves to form amicelle. The mixture was further stirred for two days and nights with astirrer, and then the micelle solution (dispersed solution) thusobtained was subjected to centrifugal separation at 2,000 rpm for 30minutes.

A visible absorption spectrum of the supernatant is shown in FIG. 6(Mark A). This confirmed that phthalocyanine was soluble (dispersed) inthe micelle solution. The solubility of phthalocyanine was 8.1 mM/2 mMmicelle forming agent solution.

To this solution, lithium bromide as a supporting salt was added so thatthe concentration would be 0.1 M and stirred for 10 minutes with astirrer.

With the use of the solution as an electrolyte, an ITO transparent glasselectrode as an anode, platinum as an cathode and a saturated calomelelectrode as a reference electrode, constant electric potentialelectrolysis was carried out at 25° C. at the applied voltage of 0.5 V,and an electric current density of 18 μA/cm² for 30 minutes. The amountof electricity passed in that period was 0.03 C.

As the result, a thin film of phthalocyanine was found on the ITOtransparent glass electrode. A visible absorption spectrum ofphthalocyanine on the ITO transparent glass electrode is shown in FIG. 6(Mark B). Since FIG. 6 (Mark A) agreed with FIG. 6 (Mark B), it wasconfirmed that the thin film on the ITO transparent glass electrode wasphthalocyanine. A UV absorption spectrum showed that the thickness ofthe thin film was 1.2 μm.

Further, as the result of cyclic voltammetry, the oxidation-reductionpotential was 0.183 V, and the difference between the peak potentials ofoxidation and reduction was 47 mV, which showed that the efficiency ofoxidation-reduction was improved compared with that in ComparativeExample 1 to be mentioned later.

PREPARATION EXAMPLE 4

(1) In the presence of 64.6 g of anhydrous aluminum chloride, 29.0 g ofbenzene bromide and 25.0 g of anhydrous glutaric acid were reacted atroom temperature for 8 hours in a methylene chloride solvent. Aftercompletion of the reaction, the reaction mixture was subjected tomethylene chloride extraction, alkali extraction and acid treatmentwhile treated with dilute hydrochloric acid, to obtain 39.4 g of thecompound (1) represented by the formula: ##STR69## (2) In the presenceof zinc amalgam prepared from 32.7 g of zinc and 13.6 g of mercuricchloride, 20.0 g of the above compound (1) was refluxed for 5 hours in amixed solvent of concentrated hydrochlorice acid and1,2-dimethoxyethane.

After completion of the reaction, the reaction mixture was repeatedlysubjected to ether extraction, alkali extraction, and acid treatment toobtain 15.1 g of the compound (2) represented by the formula: ##STR70##(3) An amount of 16.5 g of acid chloride of the compound (2) preparedfrom 15.0 g of the compound (2) and 50 ml of thionyl chloride, 10.6 g ofanhydrous aluminum chloride, and 11.2 g of ferrocene were reacted at 5°C. for 4 hours in a methylene chloride solvent. After completion of thereaction, the reaction mixture was treated with dilute hydrochloricacid, then purified with silica gel column chromatography, to obtain10.3 g of the compound (3) represented by the formula: ##STR71## (4) Inthe presence of zinc amalgam prepared from 10.9 g of zinc and 4.5 g ofmercuric chloride, 10.3 g of above compound (3) was refluxed for 5 hoursin a mixed solvent of concentrated hydrochloric acid and ethanol.

After completion of the reaction, the reaction mixture was purified withsilica gel column, to obtain 5.1 g of the compound (4) represented bythe formula: ##STR72##

EXAMPLE 7

To 30.0 g of polyethylene glycol (average molecular weight, 600), 0.25 gof metallic sodium was added and stirred at 100° C. for one day andnight. Then, 2.0 g of the above compound (4) 25 ml of γ-collidine and0.5 g of copper (I) iodide were added thereto and reacted at 170° C. for30 hours.

This reaction mixture was extracted with a mixture of equal amounts ofwater and n-butanol. The extract was washed with water and then wassubjected to chromatographic purification by developing on a silica gelcolumn using a mixture of ethyl acetate and methanol (ethyl acetate:methanol=4:1) as a solvent.

For the purified product obtained after drying, the yield was 33% andthe amount was 1.5 g. The elemental analytical values were : carbon,61.5%; hydrogen, 9.0%. The results measuring proton nuclear magneticresonance spectrum (¹ H-NMR) were as shown in FIG. 7.

From the results above, it can be seen that the above purified productwas a ferrocene derivative having the following structure: ##STR73##

PREPARATION EXAMPLE 5

An amount of 3.0 g of compound (4) prepared in Preparation Example 4 (4)and 0.8 g of the copper (I) cyanide were heat-refluxed for 6 hours in adimethyl formamide solvent. The hot mixture was treated with water, theresulting precipitate was treated with a warm aqueous solution ofethylenediamine. Then, a precipitate was extracted with benzene, washedwith water, dried and concentrated.

The residue obtained and 1.3 g of potassium hydroxide were refluxed for8 hours in a mixed solvent of ethanol and water. After completion of thereaction, the reaction mixture was treated with dilute hydrochloricacid, extracted with ethyl acetate, and then purified with a silica gelcolumn chromatography to obtain 2.1 g of the following compound (5):##STR74##

EXAMPLE 8

The procedure of Example 7 was repeated except that 34.0g ofpolyethylene glycol (average molecular weight, 600) and 0.5 cc ofconcentrated sulfuric acid were added to 2.1 g of the above compound (5)and reacted at 80° C. for 8 hours.

For the purified product obtained, the yield was 37% and the amount was2.0 g. The elemental analytical values were: carbon, 60.9%; hydrogen,7.9%. The results of measurement of ¹ H-NMR were as shown in FIG. 8.

From the above results, it can be seen that the above purified productwas a ferrocene derivative having the following structure: ##STR75##

PREPARATION EXAMPLE 6

(1) In the presence of 21.6 g of anhydrous aluminum chloride, 25.1 g offerrocene and 25.4 g of 4-bromo butyryl chloride were reacted at 5° C.for 2 hours in a methylene chloride solvent. After completion of thereaction, the reaction mixture was treated with dilute hydrochloric acidand then purified with a silica gel column to obtain 20.7 g of thefollowing compound (6). ##STR76## (2) In the presence of zinc amalgamprepared from 26.2 g of zinc and 10.9 g of mercuric chloride, 20.7 g ofthe above compound (6) was reacted at 80° C. for 3 hours in a mixedsolvent of concentrated hydrochloric acid and ethanol. After completionof the reaction, the reaction mixture was extracted with ethyl acetateand purified with a silica gel column to obtain 6.1 g of the followingcompound (7): ##STR77## (3) In the presence of 0.3 g of tetra n-butylammonium fluoroborate, 2.7 g of the above compound (7) and 3.0 g ofsodium azide were reacted at 100° C. for 7 hours in a water solvent.After completion of the reaction, the reaction mixture was extractedwith ether and dried.

To the dried ether solution, 2.5 g of lithium aluminum hydride was addedand refluxed for 5 hours and then treated with water to obtain 1.9 g ofthe following compound (8). ##STR78## (4) In the presence of 1.4 g oftriethylamine, 1.9 g of the following compound (8) and 1.5 g ofterephthalic acid methylester chloride were reacted for 4 hours in atoluene solvent at room temperature. After completion of the reaction,the reaction mixture was treated with water, extracted with ethylacetate and then purified with a silica gel column to obtain 2.6 g ofthe following compound (9). ##STR79## (5) An amount of 2.6 g of theabove compound (9) and 0.7 g of potassium hydroxide were reacted at 50°C. for one hour in an ethanol solvent. After completion of the reaction,the reaction mixture was concentrated to obtain 2.3 g of the followingcompound (10). ##STR80##

EXAMPLE 9

The procedure of Example 7 was repeated except that to 2.3 g of theabove compound (10) 35 g of polyethylene glycol (average molecularweight, 600) and 0.5 cc of concentrated sulfuric acid were added andreacted at 90° C. for 8 hours.

For the purified product, the yield was 28% and the amount was 1.6 g.The elemental analytical values were: carbon, 59.4%; hydrogen, 7.4%;nitrogen, 1.3%.

The results of the measurement of ¹ H-NMR were as shown in FIG. 9.

From the above purified results, it can be seen that the above purifiedproduct was a ferrocene derivative having the following structure:##STR81##

EXAMPLE 10

Into 100 cc of water was added a micelle forming agent composed offerrocene derivative obtained in Example 7 to make a 2 mM solution. To20 cc of the resulting micelle solution, 0.1 g of phthalocyanine(produced by Tokyo Kasei) was added and stirred by ultrasonic waves for10 minutes to disperse and dissolve, followed by stirring for 2 days andnights with a stirrer. Then, the dispersed and soluble micelle solutionwas subjected to centrifugal separation for 30 minutes at 2000 rpm.

A visible absorption spectrum of the supernatant confirmed thatphthalocyanine was dispersed. Its absorbance shows that the solubilityof phthalocyanine was 8.4 mM/2 mM micelle forming agent.

Into the dispersed and soluble micelle solution, lithium bromide wasadded so that the concentration became 0.1 M, and was stirred with astirrer for 10 minutes. By using this solution as an electrolyte, an ITOtransparent glass electrode as the anode, platinum as the cathode and asaturated calomel electrode as the reference electrode, constantpotential electrolysis was carried out at 25° C. at the applied voltageof 0.5 V and an electric current density of 8.6 μA/cm² for 30 minutes.The amount of electric current passed in that period was 0.015 C.

As a result, a thin film of phthalocyanine was formed on the ITOtransparent glass electrode.

Since the absorption spectrum on the ITO transparent glass electrodeagreed with that of the dispersed and soluble micelle solution, it canbe seen that the thin film on the ITO transparent electrode wasphthalocyanine and the thickness of the film was 1.8 μm from theabsorbance.

Into the micelle solution, lithium bromide was added as a supportingsalt so that the concentration became 0.1 M. As the result of cyclicvoltammetry, the oxidation-reduction potential was 0.226 V, and thedifference between the peak voltage of oxidation and reduction was 117mV, which shows that the efficiency of oxidation-reduction was improvedcompared with that in Comparative Example 1 to be mentioned later.

EXAMPLE 11

Into 100 cc of water was added a micelle forming agent composed of theferrocene derivative obtained in Example 8 to make a 2 mM solution. To20 cc of the resulting micelle solution, 0.1 g of phthalocyanine(produced by Tokyo Kasei) was added and stirred by ultrasonic wave for10 minutes to disperse and dissolve, followed by stirring for 2 days andnights with a stirrer. Then, the dispersed and soluble micelle solutionwas subjected to centrifugal separation for 30 minutes at 2000 rpm.

A visible absorption spectrum of the supernatant confirmed thatphthalocyanine was dispersed. Its absorbance shows that the solubilityof phthalocyanine was 8.2 mM/2 mM micelle forming agent.

Into the dispersed and soluble micelle solution, lithium bromide wasadded so that the concentration became 0.1 M, and was stirred with astirrer for 10 minutes. By using this solution as an electrolyte, an ITOtransparent glass electrode as the anode, platinum as the cathode and asaturated calomel electrode as the reference electrode, constantpotential electrolysis was carried out at 25° C. at the applied voltageof 0.5 V and an electric current density of 11.2 μA/cm² for 30 minutes.The amount of electric current passed in that period was 0.02 C.

As a result, a thin film of phthalocyanine was formed on the ITOtransparent glass electrode.

Since the absorption spectrum on the ITO transparent glass electrodeagreed with that of the dispersed and soluble micelle solution, it canbe seen that the thin film on the ITO transparent electrode wasphthalocyanine and the thickness of the film was 2.5 ∥m from theabsorbance.

EXAMPLE 12

Into 100 cc of water was added a micelle forming agent composed of theferrocene derivative obtained in Example 9 to make 2 mM solution. To 20cc of the resulting micelle solution, 0.1 g of phthalocyanine (producedby Tokyo Kasei) was added and stirred by ultrasonic wave for 10 minutesto disperse and dissolve, followed by stirring for 2 days and nightswith a stirrer. Then, the dispersed and soluble micelle solution wassubjected to centrifugal separation for 30 minutes at 2000 rpm.

A visible absorption spectrum of the supernatant confirmed thatphthalocyanine was dispersed. Its absorbance shows that the solubilityof phthalocyanine was 8.5 mM/2 mM micelle forming agent.

Into the dispersed and soluble micelle solution, lithium bromide wasadded so that the concentration became 0.1 M, and was stirred with astirrer for 10 minutes. By using this solution as an electrolyte, an ITOtransparent glass electrode as the anode, platinum as the cathode and asaturated calomel electrode as the reference electrode, controlledpotential electrolysis was carried out at 25° C. at the applied voltageof 0.5 V and an electric current density of 13.1 μA/cm² for 30 minutes.The amount of electric current passed in that period was 0.02 C.

As a result, a thin film of phthalocyanine was formed on the ITOtransparent glass electrode.

Since the absorption spectrum on the ITO transparent glass electrodeagreed with that of the dispersed and soluble micelle solution, it canbe seen that the thin film on the ITO transparent electrode wasphthalocyanine and the thickness of the film was 2.6 μm from theabsorbance.

COMPARATIVE EXAMPLE 1

Into 100 cc of water was added the compound (FPEG), represented by theformula: R1 ? ##STR82## as a surfactant (micelle forming agent) to makea 2 mM solution. To 20 cc of the resulting micelle solution, 0.1 g ofphthalocyanine was added and stirred by ultrasonic wave for 10 minutesto disperse and dissolve, followed by stirring for 2 days and nightswith a stirrer. Then, the micelle solution (dispersed solution) wassubjected to centrifugal separation for 30 minutes at 2000 rpm.

A visible absorption spectrum of the supernatant confirmed thatphthalocyanine was soluble (dispersed) in the micelle solution. Thesolubility of phthalocyanine was 4.1 mM/2 mM micelle forming agent.

Into this solution, lithium bromide was added as a supporting salt sothat the concentration became 0.1 M, and was stirred with a stirrer for10 minutes.

By using this solution as an electrolyte, an ITO transparent glasselectrode as the anode, platinum as the cathode and a saturated calomelelectrode as the reference electrode, constant potential electrolysiswas carried out at 25° C. at the applied voltage of 0.5 V and anelectric current density of 17.2 μA/cm² for 30 minutes. The amount ofelectric current passed in that period was 0.07 C.

As a result, a thin film of phthalocyanine was formed on the ITOtransparent glass electrode. It can be seen that the thickness of thethin film of phthalocyanine was 1.0 μm from the UV absorption spectrum.

As the result of cyclic voltammetry, the oxidation reduction potentialwas 0.260 V, and the difference between the peak voltage of oxidationand reduction was 70 mV.

PREPARATION EXAMPLE 7 (1) In the presence of 14.6 g of anhydrousaluminum chloride, 9.4 g of ferrocene and 10.0 g of 2-phenyl glutaricanhydride were reacted for 2 hours at room temperature in a methylenechloride solvent.

After completion of the reaction, the reaction mixture was treated withdilute hydrochloric acid and then extracted with methylene chloride,with alkali, treated with acid to obtain 16.6 g of the isomer mixture ofthe following compound (11) and (12) (yield, 86%). ##STR83## (2) In thepresence of zinc amalgam prepared from 9.6 g of zinc and 4.4 g ofmercuric chloride, 8.3 g of the mixture of the compounds (11) and (12)were reacted at 80° C. for 2 hours in a mixed solvent of concentratedsulfuric acid and 1,2-dimethoxy ethane.

After completion of the reaction, the reaction mixture was extractedwith ethyl acetate and purified with a silica gel column to obtain 3.9 gof the isomer mixture of the following compounds (13) and (14) (yield,49%). ##STR84##

EXAMPLE 13

To 3.9 g of the isomer mixture of the compounds (13) and (14) obtainedin Preparation Example 7, 66 g of polyethylene glycol (average molecularweight, 600) and 0.5 ml of concentrated sulfuric acid were added andreacted at 80° C. for 8 hours.

The reaction mixture was extracted with a mixture of equal amounts ofwater and n-butanol. The extract was washed with water and then wassubjected to chromatographic purification by developing on a silica gelcolumn using a mixture of ethyl acetate and methanol (4:1) as adeveloping solvent.

For the purified product obtained after drying, the amount was 3.5 g(yield, 34%). The elemental analytical values were: carbon, 61.0%;hydrogen, 8.2%. The results of the measurement of ¹ H-NMR were as shownin FIG. 10.

From the above results, it was identified that the above purifiedproduct was a ferrocene derivative having the following structure(isomer). ##STR85##

EXAMPLE 14

Into 100 cc of water was added ferrocene derivative obtained in Example13 to make a 2 mM solution. To 20 cc of the resulting micelle solution,0.1 g of phthalocyanine (produced by Tokyo Kaeei) was added and stirredby ultrasonic wave for 10 minutes to disperse and dissolve, followed bystirring for 2 days and nights with a stirrer. Then, the dispersed andsoluble micelle solution was subjected to centrifugal separation for 30minutes at 2000 rpm. A visible absorption spectrum of the supernatantconfirmed that phthalocyanine was dispersed. Its absorbance shows thatthe solubility of the micelle forming agent was 8.4 mM/2 mM micelleforming agent.

Into dispersed and soluble micelle solution, lithium bromide was addedso that the concentration became 0.1 M, and was stirred with a stirrerfor 10 minutes. By using this solution as an electrolyte, an ITOtransparent glass electrode as the anode, platinum as the cathode and asaturated calomel electrode as the reference electrode, constantpotential electrolysis was carried out at 25° C. at the applied voltageof 0.5 V and an electric current density of 9.8 μA/cm² for 30 minutes.The amount of electric current passed in that period was 0.015 C.

As a result, a thin film of phthalocyanine was formed on the ITOtransparent glass electrode. Since the absorption spectrum on the ITOtransparent glass electrode agreed with that of the dispersed andsoluble micelle solution, it can be seen that the thin film on the ITOtransparent glass electrode was phthalocyanine and the thickness of thefilm was 2.2 μm from the absorbance.

Again, the to micelle solution, lithium bromide was added as asupporting salt so that the concentration became 0.1 M. As the result ofcyclic voltammetry, the oxidation-reduction potential was 0.192 V, andthe difference between the peak voltage of oxidation and reduction was60 mV.

PREPARATION EXAMPLE 8

(1) In the presence of 1 cc of sulfuric acid, 8.0 g of the mixture ofthe compounds (11) and (12) obtained in Preparation Example 7 (1) wasrefluxed for 5 hours in an ethanol solvent. After completion of thereaction, the reaction mixture was concentrated, treated with alkali,extracted with ether and after drying, the resulting ether was distilledaway to obtain 8.1 g of isomer mixture of the following compounds (15)and (16). ##STR86## (2) An amount of 8.1 g of the mixture of thecompounds (15) and (16) obtained in (1) above, 8.0 g of anhydrousaluminum chloride and 3.8 g of sodium borohydride were refluxed for 2hours in a tetrahydrofuran solvent. After completion of the reaction,the reaction mixture was treated with dilute hydrochloric acid andextracted with ethyl acetate and then purified with a silica gel columnto obtain 4.2 g of the isomer mixture of the following compounds (17)and (18) (yield, 60%). ##STR87## (3) An amount of 4.2 g of the mixtureof the compounds (17) and (18) obtained in (2) above, 4.7 g oftriphenylphosphine and 6.0 g of carbon tetrabromide were refluxed for 3hours in a chloroform solvent. After completion of the reaction, thereaction mixture was concentrated, extracted with n-pentane and purifiedwith a silica gel column to obtain 3.4 g of the isomer mixture of thefollowing compounds (19) and (20) (yield, 69%). ##STR88##

EXAMPLE 15

Into 42 g of polyethylene glycol (average molecular weight, 1000), 0.30g of metallic sodium was added and stirred at 80° C. for one day andnight. Then, 3.3 g of isomer mixture of the compounds (19) and (20)obtained in Preparation Example 8 (3) was added thereto and reacted at110° C. for 10 hours. The reaction mixture was extracted with a mixtureof equal amounts of water and n-butal. The extract was washed with waterand then was subjected to chromatographic purification by developing ona silica gel column using a mixture of ethyl acetate and methanol (4:1)as a developing solvent.

For the purified product obtained, the amount was 3.9 g (yield, 37%),and the elemental analytical values were: carbon, 58.5%; hydrogen, 8.1%.The results of the measurement of ¹ H-NMR were as shown in FIG. 11.

From the above results, it was identified that the above purifiedproduct was a ferrocene derivative having the following structure(isomer). ##STR89##

EXAMPLE 16

Into 100 cc of water was added the ferrocene derivative obtained inExample 15 to make a 2 mM solution. To 20 cc of the resulting micellesolution, 0.1 g of phthalocyanine (produced by Tokyo Kasei) was addedand stirred by ultrasonic wave for 10 minutes to dissolve, followed bystirring for 2 days and nights with a stirrer. Then, the dispersed andsoluble micelle solution was subjected to centrifugal separation for 30minutes at 2000 rpm. A visible absorption spectrum of the supernatantconfirmed that phthalocyanine was dispersed. Its absorbance shows thatthe solubility of the micelle forming agent was 7.9 mM/2 mM micelleforming agent.

Into dispersed and soluble micelle solution, lithium bromide was addedso that the concentration became 0.1 M, and was stirred with a stirrerfor 10 minutes.

By using this solution as an electrolyte, an ITO transparent glasselectrode as the anode, platinum as the cathode and a saturated calomelelectrode as the reference electrode, constant potential electrolysiswas carried out at the applied voltage of 0.5 V and an electric currentdensity of 9.4 μA/cm² for 30 minutes. The amount of electric currentpassed in that period was 0.02 C.

As a result, a thin film of phthalocyanine was formed on the ITOtransparent glass electrode. Since the absorption spectrum on the ITOtransparent glass electrode agreed with that of the dispersed andsoluble micelle solution, it can be seen that the thin film on the ITOtransparent electrode was phthalocyanine and the thickness of the filmwas 1.9 μm from the absorbance.

Again into micelle solution lithium bromide was added as a supportingsalt so that the concentration became 0.1 M. As the result of cyclicvoltammetry, the oxidation-reduction potential was 0.189 V, and thedifference between the peak voltage of oxidation and reduction was 55mV.

What is claimed is:
 1. A ferrocene compound represented by the formula:##STR90## wherein A indicates ##STR91## wherein X is --CH₂ --, --O--,##STR92## G is a hydrogen atom, a methyl group, or an ethyl group, R⁴ isa hydrogen atom, a methyl group or an ethyl group, and m is a positiveinteger satisfying the expression 0≦k+m≦10,Z is --O-- or ##STR93## andR¹ and R² are identical or different and each is H, NH₂, N(CH₃)₂, CH₃,CH₃ O, OH or a halogen atom, and R³ is a hydrogen atom or a methylgroup, k is a positive integer satisfying the expression 0≦k+m≦10, and nis a real number of 2 to 70, a is an integer of 1 to 4, and b is aninteger of 1 to
 5. 2. The ferrocene compound as claimed in claim 1,represented by the formula: ##STR94## wherein k is a positive integersatisfying 0≦k≦10 and m=0 .
 3. The ferrocene compound as claimed inclaim 1, represented by the formula: ##STR95##
 4. The ferrocene compoundas claimed in claim 1, wherein R¹ and R² are identical or different andeach is a halogen atom selected from the group consisting of chlorine,bromine and fluorine.
 5. The ferrocene compound as claimed in claim 1,wherein k is 1 to
 5. 6. The ferrocene compound as claimed in claim 1,wherein m is 1 to
 5. 7. The ferrocene compound as claimed in claim 1,wherein the compound is of the formula ##STR96##
 8. The ferrocenecompound as claimed in claim 1, wherein the compound is of the formula##STR97##
 9. The ferrocene compound as claimed in claim 1, wherein thecompound is of the formula ##STR98##
 10. The ferrocene compound asclaimed in claim 1, wherein the compound is of the formula ##STR99## 11.The ferrocene compound as claimed in claim 1, wherein the compound is ofthe formula ##STR100##
 12. The ferrocene compound as claimed in claim 1,wherein the compound is of the formula ##STR101##
 13. The ferrocenecompound as claimed in claim 1, wherein the compound is of the formula##STR102##
 14. The ferrocene compound as claimed in claim 1, wherein thecompound is of the formula ##STR103##
 15. The ferrocene compound asclaimed in claim 1, wherein the compound is of the formula ##STR104##16. The ferrocene compound as claimed in claim 1, wherein the compoundis of the formula ##STR105##
 17. The ferrocene compound as claimed inclaim 1, wherein the compound is of the formula ##STR106##
 18. Theferrocene compound as claimed in claim 1, wherein the compound is of theformula ##STR107##
 19. The ferrocene compound as claimed in claim 1,wherein the compound is of the formula ##STR108##
 20. The ferrocenecompound as claimed in claim 1, wherein the compound is of the formula##STR109##
 21. The ferrocene compound as claimed in claim 1, wherein thecompound is of the formula ##STR110##
 22. The ferrocene compound asclaimed in claim 1, wherein the compound is of the formula ##STR111##23. The ferrocene compound as claimed in claim 1, wherein the compoundis a compound selected from the group consisting of ##STR112##
 24. Theferrocene compound as claimed in claim 1, wherein the compound is acompound selected from the group consisting of ##STR113##